# US 12,006,477 B2 · Methods for improving heavy oils > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 12,006,477 B2 - Document ID: US12006477B2 - Status: Granted - Kind: B2 - Application number: 18/116,507 - Filed: 2023-03-02 - Published: 2023-06-29 - Granted: 2024-06-11 - Earliest claimed: 2016-05-10 - Assignees: Petroraza SAS - Applicants: Petroraza SAS - Inventors: Jose Edgar Patino - Web page: https://patentgrep.com/patent/US12006477B2 ## CPC - C10G 11/04: Oxides - C10G 2300/4037: In-situ processes - E21B 43/24: using heat, e.g. steam injection - E21B 43/305: {comprising at least one inclined or horizontal well} - C10G: CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION (cracking to hydrogen or synthesis gas C01B; cracking or pyrolysis of hydrocarbon gases to individual hydrocarbons or mixtures thereof of definite or specified constitution C07C; cracking to cokes C10B); RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES - E21B: EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS ## Abstract Novel catalysts comprising nickel oxide nanoparticles supported on alumina nanoparticles, methods of their manufacture, heavy oil compositions contacted by these nanocatalysts and methods of their use are disclosed. The novel nanocatalysts are useful, inter alia, in the upgrading of heavy oil fractions or as aids in oil recovery from steam-assisted well reservoirs. ## Claims ### Claim 1 A method for upgrading heavy oil in a steam-assisted heavy oil well, comprising: contacting the heavy oil that is contained in a rock formation associated with a steam-assisted well for producing the heavy oil, said well comprising a producer leg and an injector leg; wherein said contacting of the heavy oil includes contacting with a nanocatalyst for a time and under conditions sufficient to increase the H/C ratio (hydrogen/carbon ratio) of the heavy oil recovered from the well, wherein said nanocatalyst is steam-injected into the well injector leg or into the producer leg and injector leg; said nanocatalyst comprising: nickel oxide nanoparticles supported on alumina nanoparticles; wherein the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 99 to about 400; and Group VIII metal oxide nanoparticles supported on alumina nanoparticles, wherein the Group VIII metal oxide nanoparticles are other than nickel nanoparticles; wherein the alumina nanoparticle to Group VIIIB metal oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 99 to about 400; wherein the particle size of the alumina nanoparticle is in a range of from about 30 to about 100 nanometers; wherein the catalyst does not further comprise silver nanoparticles supported on the alumina nanoparticles; and wherein the alumina nanoparticles are present in an amount of at least 99% by weight of the catalyst. ### Claim 2 (depends on 1) A method according to claim 1, wherein the Group VIIIB metal oxide nanoparticles comprise Pd. ### Claim 3 (depends on 2) A method according to claim 2, wherein said nanocatalyst is steam-injected into the well injector leg. ### Claim 4 (depends on 2) A method according to claim 2, wherein said nanocatalyst is steam-injected into the producer leg and injector leg. ### Claim 5 (depends on 4) A method according to claim 4, wherein an injector leg/producer leg weight ratio of injected nanocatalyst is in a range of from about 55/45 to about 95/5 based on the weight of the nanocatalyst. ### Claim 6 (depends on 2) A method according to claim 2, wherein said producer and injector legs of said well are substantially parallel to each other and positioned substantially horizontally within the rock formation, with said producer leg positioned below the injector leg in the rock formation. ### Claim 7 (depends on 2) A method according to claim 2, wherein a portion of the rock formation is steam-heated to a temperature in a range of from about 220° C. to about 500° C. ### Claim 8 (depends on 7) A method according to claim 7, wherein a portion of the rock formation is steam-heated to a temperature in a range of from about 220° C. to about 345° C. ### Claim 9 (depends on 8) A method according to claim 8, wherein a portion of the rock formation is steam-heated to a contacting temperature in a range of from about 220° C. to about 300° C. ### Claim 10 (depends on 7) A method according to claim 7, wherein a portion of the rock formation is steam-heated to a contacting temperature in a range of from about 300° C. to about 500° C. ### Claim 11 (depends on 7) A method according to claim 7, wherein the rock formation is thereafter maintained in a static condition for a period of from about 2 months to about 4 months. ### Claim 12 (depends on 11) A method according to claim 11, wherein the rock formation is thereafter maintained in a static condition for a period of from about 2 months to about 3 months. ### Claim 13 (depends on 11) A method according to claim 11, wherein after a portion of the heavy oil is extracted, the injector leg is further heated under pressure with steam for a time and under conditions to make up for a well pressure loss or well temperature loss, said further pressurized steam insufficient to cause any additional fracturing of the rock formation. ### Claim 14 (depends on 6) A method according to claim 6, wherein the injector leg/producer leg weight ratio of injected nanocatalyst is in a range of from about 65/35 to about 95/5 based on the weight of the nanocatalyst. ### Claim 15 (depends on 14) A method according to claim 14 wherein the injector leg/producer leg weight ratio of injected nanocatalyst is in a range of from about 85/15 to about 95/5 based on the weight of the nanocatalyst. ### Claim 16 (depends on 2) A heavy oil prepared by the method according to claim 2, wherein the H/C ratio of the produced heavy oil is larger than the heavy oil contained in a rock formation prior to the contacting with the nanocatalyst. ### Claim 17 (depends on 2) A method according to claim 2, wherein the heavy oil in the well is retreated by contacting with a retreatment nanocatalyst for a time and under conditions sufficient to increase the H/C ratio (hydrogen/carbon ratio) of the heavy oil recovered from the well, wherein said retreatment nanocatalyst is steam-injected into the well injector leg or into the producer leg and injector leg; said retreatment nanocatalyst comprising: nickel oxide nanoparticles supported on alumina nanoparticles; wherein the alumina nanoparticle to nickel oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 99 to about 400; and Group VIII metal oxide nanoparticles supported on alumina nanoparticles, wherein the Group VIII metal oxide nanoparticles are other than nickel nanoparticles; wherein the alumina nanoparticle to Group VIIIB metal oxide nanoparticle weight to weight ratio in the catalyst is in a range of from about 99 to about 400; wherein the particle size of the alumina nanoparticle is in a range of from about 30 to about 100 nanometers; wherein the catalyst does not further comprise silver nanoparticles supported on the alumina nanoparticles; and wherein the alumina nanoparticles are present in an amount of at least 99% by weight of the catalyst. ### Claim 18 (depends on 17) A method according to claim 17, wherein the nickel oxide (NiO) nanoparticles in the retreatment nanocatalyst are present in an amount of about 0.2% to about 1% by weight of catalyst. ### Claim 19 (depends on 17) A method according to claim 17, wherein the retreatment contacting does not exceed the intrinsic fracture pressure of the oil well. ### Claim 20 (depends on 5) A method according to claim 5, wherein, subsequent to said retreatment contacting, the well is maintained in a static condition for a period of time before heavy oil removal is initiated.